Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C3/00—Pulping cellulose-containing materials
  • D21C3/22—Other features of pulping processes
  • D21C3/222—Use of compounds accelerating the pulping processes
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C3/00—Pulping cellulose-containing materials
  • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/10—Bleaching ; Apparatus therefor

Definitions

• This invention relates to compositions and methods for the production of enhanced pulp in chemical pulping processes. More particularly, this invention relates to compositions and methods for producing enhanced pulp in the Kraft pulp process. This invention further relates to compositions and methods for improving the pulp production rate in chemical pulping processes.
• pulp making is carried out on a large scale. Accordingly, it is highly desirable that such pulp making operations be carried out in a cost effective, efficient operation with minimum equipment downtime and with minimum periods of reduced process equipment operating efficiency. It is further desired to produce wood pulp of high strength, quality and high yield.
• the basic steps in industrial pulp making are to convert plant fiber into chips, convert chips into pulp, (optionally) bleach the pulp, wash the pulp, and transform the pulp into suitable paper which can be used in paper products such as writing paper, newsprint and paper for documents.
• a digester which is a vessel or tank for holding the chips and an aqueous digesting composition and which can be operated in either a batch or continuous mode as desired).
• the digester is sealed and the digester composition is heated to a suitable cook temperature, e.g. temperatures up to about 180°C, under high pressure.
• a suitable cook temperature e.g. temperatures up to about 180°C
• the digester contents (pulp and black liquor) are transferred to a holding tank.
• the pulp in the holding tank is transferred to the brown stock washers while the liquid (black liquor formed in the digester) is sent to the black liquor recovery area.
• the black liquor is evaporated to a high solids content, usually 60-80% solids.
• MEE multiple effect evaporators
• These evaporators generally range from four to eight effects in length.
• the Kraft cook is highly alkaline, usually having a pH of 10 to 14, more particularly 12 to 14.
• the digester composition contains a large amount of sodium sulfide, which is used as an accelerant to increase the delignification rate of the cook. This works to release most of the lignin in the wood chips and thus the cellulose and part of the hemicellulose become available as pulp.
• pulping process and subsequent bleaching processes are separate operations. There are several bleaching sequences that are used commercially. Chlorine, chlorine dioxide, sodium hypochlorite, hydrogen peroxide, oxygen, ozone and mixtures thereof are employed in many bleaching processes.
• pulp recovered from the digester process is treated with the following steps: (a) chlorine dioxide, (b) caustic extraction, (c) chlorine dioxide, (d) caustic extraction, and (e) chlorine dioxide to reach the final pulp brightness.
• AOX absorbable organic halide
• One approach to generate Kraft pulps with low lignin content is by using an extended delignification process.
• Extended delignification processes require extensive equipment changes (additional cooking vessels) and may result in higher facility energy requirements. Additionally, a major concern with extended delignification is to achieve decreased lignin content while minimizing cellulose damage. Cellulose damage is reflected in lower pulp viscosity and lower pulp strength.
• compositions for use in chemical pulping processes and an improved chemical pulping process have now been discovered that achieve one or more of the desired pulp property or process throughput improvements.
• an aqueous composition for improving properties of pulp produced in a kraft digestes reducing the digester cycle time, or reducing the pulping or bleaching chemicals required in alkaline chemical pulping processes comprising the alkaline composition of the digester of said process comprising wood chips, sodium hydroxide and sodium sulfide and an effective amount of at least one compound selected from the group consisting of:
• the wood chips that can be processed into pulp using the composition and chemical pulping process of the invention can be either hardwoods, softwoods or mixtures thereof.
• Suitable hardwoods include, but are not limited to, aspen, birch, cottonwood, poplar, maple, and the like, and mixtures thereof.
• Suitable softwoods include, but are not limited to, pine (e.g. red pine, jack pine, and Southern yellow pine), spruce, balsam fir, Douglas fir, and the like, and mixtures thereof.
• a first embodiment of the invention relates to an aqueous composition for improving properties of pulp produced in a kraft digester reducing the digester cycle time, or reducing the pulping or bleaching chemicals required in alkaline chemical pulping processes said composition comprising the akaline composition of the digester of said process comprising wood chips, sodium hydroxide and sodium sulfide and an effective amount of at least one compound selected from the group consisting of :
• M is preferably hydrogen or alkali metal, and the alkali metal is preferably sodium or potassium
• X is -CH 2 PO 3 M 2
• Y is preferably -PO 3 M 2
• R' is preferably an alkyl group having 1 to 11 carbon atoms, more preferably 1 to 5 carbon atoms, and most preferably methyl.
• Suitable phosphonates include, but are not limited to, the phosphonates in Table 1 below.
• Table 1 below provides formulas for representative compounds of groups (I) and (II).
• the phosphonates in Table 1 are available from Solutia Inc., 575 Maryville Centre Drive, St. Louis, MO under the trademark Dequest® phosphonates and are identified by their Dequest® phosphonate product number.
• the preferred compound of formula (III) is diethylenetriamine pentaacetic acid (DTPA), or salts thereof.
• Phosphonates of formula (II) wherein R' is substituted with -SO 3 M can be prepared according to the procedures in German patent publication DE 198 57 251 A1 (June 15, 2000 ) and U.S. Patent No. 5,221,487 .
• Suitable sulfonated phosphonates of formula (II) include, but are not limited to, 1-hydroxy-3-sulfonopropan-1,1-diphosphonic acid, 2-sulfo-1-hydroxyethylidene-1,1-diphosphonic acid, 2-sulfo-1-aminoethylidene-1,1-diphosphonic acid, and salts thereof.
• Phosphonates of formula (II) wherein Z is -NR 1 R 2 can be prepared according to the procedures in U.S. Patent No. 3,979,385 and U.S. Patent No. 4,006,182 .
• Suitable phosphonates of formula (II) wherein Z is -NR 1 R 2 include, but are not limited to, 1-aminoethylidene-1,1-disphosphonic acid and salts thereof. TABLE 1 Dequest Product No.
• Dequest 2000 amino-tri(methylenephosphonic acid) N(CH 2 PO 3 H 2 ) 3
• Dequest 2006 sodium salt of amino-tri(methylenephosphonic acid) Na 5 H[N(CH 2 PO 3 ) 3
• Dequest 2010 1-hydroxyethylidene (1,1-diphosphonic acid) CH 3 C(OH)(PO 3 H 2 ) 2
• Dequest 2016 sodium salt of 1-hydroxyethylidene (1,1-diphosphonic acid) Na 4 [CH 3 C(OH)(PO 3 ) 2 ]
• Dequest 2041 - ethylenediamine tetra(methylenephosphonic acid) H 8 [(O 3 PCH 2 ) 2 NCH 2 CH 2 N(CH 2 PO 3 ) 2 ]
• Dequest 2046 - ethylenediamine tetra(methylenephosphonic acid), pentasodium salt Na 5 H 3 [(O 3 PCH 2 )
• Another preferred phosphonate of formula (I) is the compound N,N'-bis(3-aminopropyl) ethylenediamine-hexa(methylenephosphonic acid), or a salt thereof wherein the salt is sodium, potassium, ammonium and the like.
• the compound is the sodium salt
• the compound has the formula Na x H y [(O 3 PCH 2 ) 2 NCH 2 CH 2 CH 2 N(CH 2 PO 3 )CH 2 CH 2 N(CH 2 PO 3 )CH 2 CH 2 CH 2 N-(CH 2 PO 3 ) 2 ]; wherein x + y is 12, and is designated herein as 4NHMP.
• This compound can be prepared according to the procedure in Example 1 of U.S. Patent No. 5,261,491 .
• Another preferred phosphonate of formula I is a phosphonate wherein each X is -CH 2 PO 3 M 2 .
• a preferred phosphonate of formula (II) is a phosphonate wherein Y is - PO 3 M 2 and R' is alkyl of 1 to 11 carbons, more preferably 1 to 5 carbon atoms.
• a more preferred phosphonate of formula (II) is a phosphonate wherein Y is -PO 3 M 2 and R' is methyl.
• a preferred amine oxide of the phosphonate of formula (I) is - O ⁇ + N-(CH 2 PO 3 K 2 ) 3 .
• the preferred phosphonate of formula (IV) is 2-phosphonobutane-1,2,4-tricarboxylic acid.
• aqueous compositions of the invention and the effective concentration of the phosphonates or polycarboxylates of the invention will depend on many factors including, but not limited to, the type of wood, the pulping conditions in the digester, whether the pulp is to be bleached or not, and the desired pulp properties.
• the composition comprises an effective property improving amount of at least one compound described above.
• the composition comprises an amount of at least one compound described above effective to permit reduction of the cycle time and production of pulp with comparable physical properties.
• the currently preferred phosphonates of the invention are as follows:
• the currently preferred phosphonates of the invention are as follows:
• Blends of at least two compounds independently selected from the phosphonates of formulas (I), (II) and (IV), the polycarboxylate of formula (III), and the amine oxides of the phosphonates of formula (I) may be used according to the invention. It is currently preferred to use a blend of two phosphonates, with a blend of a phosphonate of formula (I) with either a phosphonate of formula (I) or formula (II) being more preferred, and a blend of a phosphonate of formula (I) with a phosphonate of formula (II) being most preferred.
• the composition of the blends can vary over a wide range with the percentage of each component ranging broadly from 1 to 99 wt.
• each phosphonate is present in an amount of at least 1 wt. %.
• each phosphonate is present in an amount of at least 10 wt. %.
• each phosphonate is present preferably in an amount of 10 to 90 wt. %, and more preferably in an amount of 20 to 80 wt. %.
• a series of blends of phosphonates which may be used according to the invention were prepared for testing.
• the blends were prepared as concentrates having 30% total active acid content and were then diluted to the desired concentration for use. These blends (as described below) were tested in a simulated Kraft cook according to the procedure described in the Examples. The weight ratios of these various blends are shown in Table 2 below. TABLE 2 BLEND NO.
• the preferred blends for use in the invention are blends of a phosphonate selected from 1-hydroxyethylidene (1,1-diphosphonic acid) or salts thereof with a phosphonate selected from the phosphonates of formulas (I). More preferred are blends of phosphonates selected from 1-hydroxyethylidene (1,1-diphosphonic acid) or salts thereof with amino-tris(methylenephosphonic acid), N,N'-bis(3-aminopropyl)ethylenediamine-hexa(methylenephosphonic acid), hexamethylenediamine tetra(methylenephosphonic acid), diethylenetriamine-penta(methylenephosphonic acid) or salts thereof.
• compositions of the invention i.e. the phosphonates, carboxylates, or mixtures thereof
• an effective amount of the compositions of the invention is employed in the digester of a chemical pulping process to improve the properties of pulp produced or reduce the digester cycle time in alkaline chemical pulping processes. That effective amount depends on the particular phosphonate(s) employed in practicing this invention and other factors including, but not limited to, wood type, the digester composition, the operating conditions (i.e. H-factor) of the digester, the mode of addition of the compounds of the invention, the composition and operating conditions in the brown stock washing area, and bleaching area, as well as other factors and conditions known to those of ordinary skill in the art. Selection of the effective amount of phosphonate or carboxylate will be readily apparent to one of ordinary skill in the art after reading this specification.
• compositions of the invention for improving the properties of pulp produced or reducing the digester cycle time in alkaline chemical pulping processes include, but are not limited to, at least one phosphonate of formula (I), at least one phosphonate of formula (II), at least one compound of formula (III), at least one phosphonate of formula (IV), amine oxides of the phosphonates of formula (I), and mixtures of the above.
• Such mixtures may comprise a mixture of at least two phosphonates of formula (I), a mixture of at least one phosphonate of formula (I) and at least one phosphonate of formula (II), or a mixture of at least two phosphonates of formula (II).
• the aqueous composition of the invention is at least one phosphonate of formula (I), at least one phosphonate of formula (II), a mixture of at least two phosphonates of formula (I), or a mixture of at least one phosphonate of formula (I) and at least one phosphonate of formula (II).
• the phosphonate(s) and the effective amount of each is as follows.
• the effective amount of phosphonate on an active acid basis is 0.05 to 1 wt. %, preferably 0.1 to 0.5 wt. %, based on the weight of wood chips (dry basis) charged to the digester.
• the effective amount of the phosphonate on an active acid basis is 0.03 to 1 wt. %, preferably 0.05 to 0.2 wt. %, based on the weight of wood chips (dry basis) charged to the digester.
• the effective amount of the phosphonate on an active acid basis is 0.03 to 1 wt. %, preferably 0.1 to 0.5 wt. %, based on the weight of wood chips (dry basis) charged to the digester.
• the effective amount of phosphonate on an active acid basis is 0.03 to 1 wt. %, preferably 0.05 to 0.5 wt. %, based on the weight of wood chips (dry basis) charged to the digester.
• the effective amount of phosphonate on an active acid basis is 0.03 to 1 wt. %, preferably 0.05 to 0.5 wt. %, based on the weight of wood chips (dry basis) charged to the digester.
• the effective amount of phosphonate on an active acid basis is 0.03 to 1 wt. %, preferably 0.05 to 0.5 wt. %, based on the weight of wood chips (dry basis) charged to the digester.
• the preferred phosphonate of formula (II) is CH 3 C(OH)(PO 3 M 2 ) 2 .
• the effective amount of amino carboxylate on an active acid basis is 0.05 to 1 wt. %, preferably 0.1 to 0.5 wt. %, based on the weight of wood chips (dry basis) charged to the digester.
• the effective amount of phosphonate on an active acid basis is 0.05 to 1 wt. %, preferably 0.1 to 0.5 wt. %, based on the weight of wood chips (dry basis) charged to the digester.
• the preferred phosphonate of formula (TV) is 2-phosphonobutane-1,2,4-tricarboxylic acid.
• the effective amount of amine oxide on an active acid basis is an amount similar to the effective amount of the corresponding phosphonate.
• the effective amount of amine oxide on an active acid basis is 0.03 to 1 wt. %, preferably 0.1 to 0.5 wt. %, based on the weight of wood chips (dry basis) charged to the digester.
• the preferred amine oxide of a phosphonate of formula (I) is - O ⁇ + N-(CH 2 PO 3 K 2 ) 3 .
• the aqueous composition of the invention is a mixture of at least two phosphonates of formula (I), the phosphonate(s) and the effective amount of each mixture is as follows:
• the second phosphonate is preferably selected from N(CH 2 PO 3 M 2 ) 3 , (M 2 O 3 PCH 2 ) 2 NCH 2 CH 2 N(CH 2 PO 3 M 2 ) 2 , (M 2 O 3 PCH 2 ) 2 N(CH 2 ) 6 N(CH 2 PO 3 M 2 ) 2 , or (M 2 O 3 PCH 2 ) 2 NCH 2 CH 2 N(CH 2 PO 3 M 2 )CH 2 CH 2 N(CH 2 PO 3 M 2 ) 2 .
• the amount of the mixture on an active acid basis is 0.03 to 1 wt. %, preferably 0.05 to 0.2 wt. %, based on the weight of wood chips (dry basis) charged to the digester.
• the amount of the mixture on an active acid basis is 0.03 to 1 wt. %, preferably 0.05 to 0.2 wt. %, based on the weight of wood chips (dry basis) charged to the digester.
• the second phosphonate is preferably selected from (M 2 O 3 PCH 2 ) 2 N(CH 2 ) 6 N(CH 2 PO 3 M 2 ) 2 , (M 2 O 3 PCH 2 ) 2 NCH 2 CH 2 N(CH 2 PO 3 M 2 )CH 2 CH 2 N(CH 2 PO 3 M 2 ) 2 , or N(CH 2 PO 3 M 2 ) 3 , and the amount of the mixture on an active acid basis is 0.03 to 1 wt. % , preferably 0.05 to 0.2 wt. %, based on the weight of wood chips (dry basis) charged to the digester.
• the amount of the mixture on an active acid basis is 0.03 to 1 wt. %, preferably 0.05 to 0.2 wt. %, based on the weight of wood chips (dry basis) charged to the digester.
• the amount of the mixture on an active acid basis is 0.03 to 1 wt. %, preferably 0.05 to 0.2 wt. %, based on the weight of wood chips (dry basis) charged to the digester.
• the preferred blends of at least two phosphonates of formula (I) are blends of (M 2 O 3 PCH 2 ) 2 NCH 2 CH 2 CH 2 N(CH 2 PO 3 M 2 )CH 2 CH 2 N(CH 2 PO 3 M 2 )-CH 2 CH 2 CH 2 N(CH 2 PO 3 M 2 ) 2 with N(CH 2 PO 3 M 2 ) 3 , (M 2 O 3 PCH 2 ) 2 NCH 2 CH 2 N(CH 2 PO 3 M 2 ) 2 , (M 2 O 3 PCH 2 ) 2 N(CH 2 ) 6 N(CH 2 PO 3 M 2 ) 2 , or (M 2 O 3 PCH 2 ) 2 NCH 2 CH 2 N(CH 2 PO 3 M 2 )CH 2 CH 2 N(CH 2 PO 3 M 2 ) 2 .
• the aqueous composition of the invention is a mixture of at least one phosphonate of formula (I) and at least one phosphonate of formula (II), the phosphonate(s) and the effective amount of each is as follows:
• the first phosphonate is selected from (M 2 O 3 PCH 2 ) 2 N(CH 2 ) 6 N(CH 2 PO 3 M 2 ) 2 , (M 2 O 3 PCH 2 ) 2 NCH 2 CH 2 N(CH 2 PO 3 M 2 ) 2 , (M 2 O 3 PCH 2 ) 2 NCH 2 CH 2 CH 2 N(CH 2 PO 3 M 2 )CH 2 CH 2 N(CH 2 PO 3 M 2 )CH 2 CH 2 CH 2 N-(CH 2 PO 3 M 2 ) 2 , or (M 2 O 3 PCH 2 ) 2 NCH 2 CH 2 N(CH 2 PO 3 M 2 )CH 2 CH 2 N(CH 2 PO 3 M 2 ) 2 , the amount of the mixture on an active acid basis is 0.03 to 1 wt.
• the amount of the mixture on an active acid basis is 0.03 to 1 wt. %, preferably 0.05 to 0.2 wt. %, based on the weight of wood chips (dry basis) charged to the digester.
• the most preferred blends of at least one phosphonate of formula (I) and at least one phosphonate of formula (II) are blends of (M 2 O 3 PCH 2 ) 2 NCH 2 CH 2 CH 2 N(CH 2 PO 3 M 2 )CH 2 CH 2 N(CH 2 PO 3 M 2 )CH 2 CH 2 CH 2 N-(CH 2 PO 3 M 2 ) 2 or N(CH 2 PO 3 M 2 ) 3 , with CH 3 C(OH)(PO 3 M 2 ) 2 .
• a second embodiment of the invention relates to a method for improving properties of pulp produced, reducing the digester cycle time, or reducing the pulping or bleaching chemicals required in alkaline chemical pulping processes comprising adding at least one compound to the alkaline aqueous mixture in the digester of the chemical pulping process, comprising wood chips, sodium hydroxide and sodium sulfide wherein the at least one compound is as described above.
• additives can be added with the compounds of the invention to the alkaline aqueous mixture in the digester.
• Typical additives include, but are not limited to, conventional additives known for use in the digester of a chemical pulping process.
• An example of a suitable additive that can be optionally added is anthroquinone.
• the aqueous composition of the invention is admixed with an alkaline, aqueous composition in the digester.
• the aqueous composition of the invention can be added to the digester using any conventional means known to those of ordinary skill in the art.
• the aqueous composition of the invention can be added directly to the digester composition or it can be introduced into one of the aqueous feed compositions being charged to the digester prior to charging of that aqueous feed composition.
• the pH in the digester of an alkaline chemical pulping process is at least 9. In the case of a Kraft process, the pH in the digester is preferably 10 to 14, and more preferably 12 to 14.
• the temperature in the digester is typically in the range of 110°C to 180°C, preferably about 150°C to 175°C.
• the aqueous composition of the invention can be added in a batch digester in any conventional manner known to one of ordinary skill in the art.
• the addition of the aqueous composition of the invention can be a bulk addition at the beginning of the digester cook cycle or during the digester cook cycle, or it can be added in multiple charges throughout the digestion cycle or continuously throughout the digester cook cycle. It is currently preferred to add the aqueous composition of the invention as a bulk charge at or near the beginning of the digester cook cycle.
• the addition of the aqueous composition of the invention will typically be added continuously to maintain the effective concentration of the compounds of the invention.
• the pulp that is recovered from the digester and washed can optionally be bleached using any conventional bleaching sequence depending on the desired end use of the pulp.
• bleaching sequences are used commercially in conjunction with chemical pulping processes. When bleaching is used, a majority of pulp mills use a 5-stage bleaching sequence. A common such bleaching sequence is the DEDED sequence. However, with the trend to reduce chlorine containing bleach steps, some pulp mills have moved to a bleaching sequence similar to DE op D or DE op P. A less common bleaching sequence is the OPD sequence.
• the definitions for the letters used in the bleaching sequences are:
• Bleaching processes are well known in the art and one of ordinary skill in the art will be able to practice any conventional bleaching sequence using pulp prepared using the process of the invention.
• the use of the compounds of the invention in the process of the invention enable production of pulp with brightness comparable to pulp produced without use of the compounds of the invention but with a reduction in the amount of bleaching chemicals used or reduction in the number of bleaching steps.
• the use of the compounds of the invention in the process of the invention enable production of pulp with improved brightness compared to pulp produced without use of the compounds of the invention.
• Viscosity is a measurement which relates viscosity of dissolved pulp to its strength properties. Mills use it as a way to test pulp properties quickly. Viscosity is related to the degree of cellulose polymerization and amount of lignin and hemicellulose attached to the fiber. Generally, as cellulose chains are broken and the lignin is removed, the viscosity decreases. The amount of damage to the fiber during the Kraft cook can be seen in the viscosity test. The compounds of the invention have been demonstrated in the examples herein to be good protectors of fiber strength during the Kraft cook.
• the benefits of achieving a higher viscosity at a given kappa number include the ability to cook a pulp longer and maintain a similar strength property or the ability to use more severe bleaching conditions to get a brighter pulp or use a process that is less expensive in chemical cost such as oxygen bleaching.
• a small increase in yield of the pulp can result in a huge savings to the pulp mill.
• a yield increase means more pulp for the same amount of wood chips. This would also have the impact of lowering solids in the black liquor recovery area. Since many pulp mills are bottlenecked in the black liquor recovery area, this would allow some pulp mills to raise production without spending capital for additional equipment.
• the use of the compounds of the invention generally result in decreasing the kappa number, so the pulp mill would have the ability to decrease the cook time or cook temperature (i.e. H-factor). Decreasing the Kraft cook temperature would result in less carbohydrate degradation. This would typically increase strength properties, viscosity and yield. Decreasing the cook time would allow a pulp mill to increase the number of Kraft cooks done in a day, i.e. increase the pulp production rate.
• cook time or cook temperature i.e. H-factor
• a Kraft cook test was employed in the following examples and illustrates the use of the process of this invention to determine the effect of the compositions of this invention as a pulp modifier in a Kraft cook. The general procedure described below was followed. Additionally, the tests were generally carried out at various concentrations as active acid based on the amount of wood chips (oven-dry basis) charged to the digester, for each inventive compound tested, and also with no added compound present.
• the active acid level is that amount of free acid which is equimolar to the amount of phosphonate or carboxylate that was actually added to the digester. Unless otherwise specified, use of "%" is on a weight basis.
• the Kraft Cook Test used herein was developed to gauge the performance of the compositions of this invention in a simulated Kraft digester composition.
• the test was a standard Kraft cook in a model MK 610 Systems Inc. minimill laboratory digester.
• the digester aqueous composition temperature was ramped from ambient temperature to 170°C in about 45 minutes and then maintained at 170°C for the remainder of the test.
• Aspen or red pine wood chips were obtained from a pulp mill in the Upper Midwestern United States. Pulping conditions were: a 4:1 liquor to wood ratio, 16-20% AA (active alkali) and 25% sulfidity.
• the H-factor length of cook was varied in the cooks.
• the amount of phosphonate or carboxylate used was also varied.
• Aspen or pine wood chips that remained on a 1 ⁇ 4-inch round-holed mesh screen were utilized in the test, while removing knots and oversize chips.
• wood chips were air dried overnight by laying them out on a counter. Wood chips not air dried were stored in a cold room at 13°C and used before they began to show signs of decay.
• a liquor to wood ratio of 4:1 was prepared with 16-20% active alkali, having a 25% sulfidity.
• the charge of phosphonate or carboxylate employed was based upon the weight of wood chips (oven-dry basis) charged to the digester to give the desired equivalent wt. % of active acid in the digester.
• White liquor was prepared according to the following procedure (for most runs), although some Kraft cooks used different AA. For an 18% AA, 25% sulfidity: 62 g caustic and 61g sodium sulfide nonahydrate were added to 500 mL water. After all chemicals were dissolved, the final dilution was added, which depended on the moisture content of the wood chips.
• the phosphonates used individually and in blends in the examples were obtained from Solutia Inc. (St. Louis, MO).
• DTPA was obtained from Dow Chemical (Versenex 80 TM ), caustic, sulfuric acid and hydrogen peroxide were from Mallinckrodt, sodium sulfide nonahydrate from EM Science, potassium chlorate and oxalic acid from Fisher Scientific, sodium thiosulfate from J.T. Baker, and the oxygen cylinders from Twin City Oxygen.
• the pulp properties of most interest in the industry are the kappa number (related to lignin content in the pulp), pulp brightness, screened yield, reject amount, and pulp strength properties.
• Pulp was prepared using the procedures described in the Kraft Cook Test section above. The pulp was thoroughly washed, so no carryover of the black liquor and/or compounds of the invention occurred.
• Pulp (30g, OD wt. basis) was bleached in doubled plastic bags at 10% consistency at 70°C using a hot water bath. Chemical dosage was varied depending on the stage. Bleaching times for Do, E 1 , D 1 , E 2 , and D 2 were 150, 60, 90, 60 and 90 minutes, respectively. Residual chlorine dioxide was tested after each D stage. The pH exiting each bleach stage was also measured.
• the D, E op , and P stages used 60, 240, and 30 g pulp (OD wt. basis), respectively.
• the bleaching times were 90, 60 and 120 minutes, respectively.
• the bleaching temperatures were 70, 90 and 85-87°C, respectively.
• the D stage used 1% chlorine dioxide on pulp.
• the E op stage used 1% peroxide, 3% caustic, 0.1% magnesium sulfate, and 30, 40 or 100 psi oxygen gas.
• This stage used both a Mark IV Quantum mixer and LS1200 Chemineer reactor for the bleaching.
• the P stage used 1% peroxide, 2% caustic, 0.1% magnesium sulfate, and 1.5% sodium silicate based on OD pulp. Residuals, end pH, and brightness were determined after each stage.
• OPD The O, P and D stages all used 60g pulp (OD wt. basis).
• the O stage used 2.5% caustic, 0.1% magnesium oxide, 90psi oxygen gas, 10 or 15% consistency, 45 minute retention time, and 90°C in a Mark IV Quantum mixer.
• the P stage used 2% caustic, 0.1% magnesium sulfate, 1.5% sodium silicate, 1.2% peroxide, 10% consistency, and 120 minutes at 85-88°C.
• the D stage used 0.8% chlorine dioxide, 0.3% caustic per 1% chlorine dioxide, and 90 minutes at 70°C. Residuals, end pH, and brightness were determined after each stage.
• Table 4 demonstrates that Dequest 2066 and DTPA at effective concentrations produce pulp with lower kappa number, higher brightness and equivalent or improved strength properties.
• Table 3 Screening Cooking Experiments on Hardwood (Aspen) Sample/ Conc. Yield, % Kappa No.
• Table 6 demonstrates that selected phosphonates of the invention produce pulp from softwood with lower kappa number and/or improved strength.
• Dequest product 2006 generally produced pulp having lower kappa number and improved strength
• Dequest product 2054 generally produced pulp with improved strength.
• Kraft cooks were performed on undried hardwood (aspen) and softwood (pine) wood chips according to the procedure described in the Pulping Description section of the Examples using either no phosphonate (control) or using inventive compound Dequest 2066 or 2006 at 0.2 wt. % (as active acid based on the weight of wood chips (dry basis) charged to the digester). The pulp was recovered and tested and the results presented in Table 7.
• R14 means that the mesh has 14 openings per square inch.
• P100 means the amount of fibers passing through the R100 mesh screen.
• Tables 10 and 11 demonstrate the impact of treating the pulp with these products in the digester. As can be seen after final pulp bleaching, the fiber length was not negatively impacted by treatment with the compounds of the invention in the digester.
• the W weighted average fiber length data in Table 11 is more useful for fiber length when making this comparison. As Dequest 2010 charge is increased, both fiber length and coarseness decrease slightly compared to the control, indicating more intense cooking of the fiber or more of the material attached to the fiber is being removed.
• Kraft cooks were performed on undried hardwood (aspen) wood chips according to the procedure described in the Pulping Description section of the Examples using either no phosphonate (control) or using Dequest 2066 at 0.2 wt. % concentration. The pulp was recovered and tested and the results presented in Table 15. The pulp was then bleached using a DEDED sequence as described in the Bleaching Description section of the Examples using the conditions set forth in Table 15. The bleached pulp was tested during and at the end of the bleaching sequence and the results presented in Table 15.
• Kraft cooks were performed on undried hardwood (aspen) wood chips according to the procedure described in the Pulping Description section of the Examples using either no phosphonate (control) or using Dequest 2066 at 0.2 wt. % concentration. The pulp was recovered and tested and the results presented in Table 16. The pulp was then bleached using a DEopD sequence as described in the Bleaching Description section of the Examples using the conditions set forth in Table 16. The bleached pulp was tested during and at the end of the bleaching sequence and the results presented in Table 16. The data in Table 16 demonstrates that Dequest 2066 produced pulps with higher initial brightness and lower kappa number. Dequest 2066 produced bleached pulp with higher viscosity and higher brightness after the DEop stage (Series #3 v. Series #6).
• Dequest 2066 also produced final bleached pulp with higher viscosity, higher yield and higher brightness (Series #4 v. Series #7).
• TABLE 15 Hardwood (Aspen) DEDED Bleaching HW-Control HW-2066(0.2%) Initial Kappa number 15.2 13.9 Initial Brightness, % 31.4 33.9 Initial Freeness @20°C, ml 665 670 General conditions Consistency 10% Temperature 70°C D1 C10 2 , % on OD pulp 1 1 Time, min 150 150 pH: Initially 3.4 3.5 End 2.69 2.52 Residual C10 2 , g/l ND ND Brightness D - - E pH: Initially 12.44 12.47 End 12.2 12.24 Brightness DE - - D2 C10 2 , % on OD pulp 1 1 Time, min 90 90 End pH 2.48 2.46 Residual C10 2 , g/l ⁇ 0.02 ⁇ 0.02 Brightness DED - - E pH: Initially 12.42 12.48 End 12.2 12.17
• Kraft cooks were performed on undried hardwood (aspen) wood chips according to the procedure described in the Pulping Description section of the Examples using either no phosphonate (control) or using Dequest 2066 at 0.2 wt. % concentration. The pulp was recovered and tested and the results presented in Table 17. The pulp was then bleached using a DEopP sequence as described in the Bleaching Description section of the Examples using the conditions set forth in Table 17. The bleached pulp was tested during and at the end of the bleaching sequence and the results presented in Table 17.
• Dequest 2066 produced pulps with higher initial brightness and lower kappa number.
• Dequest 2066 produced bleached pulp with higher viscosity and higher brightness after the DEop stage (Series #3 v. Series #6).
• Dequest 2066 also produced final bleached pulp with higher viscosity and higher brightness (Series #5 v. Series #8).
• Kraft cooks were performed on undried hardwood (aspen) wood chips according to the procedure described in the Pulping Description section of the Examples using either no phosphonate (control) or using Dequest 2066 at 0.2 wt. % concentration. The pulp was recovered and tested and the results presented in Table 18. The pulp was then bleached using a DED and DEDED sequence as described in the Bleaching Description section of the Examples using the conditions set forth in Table 18. The bleached pulp was tested during and at the end of the bleaching sequence and the results presented in Table 18.
• Dequest 2066 produced pulps with higher initial brightness and lower kappa number.
• Dequest 2066 produced bleached pulp with higher viscosity and higher brightness after the DED stage (Series #9 v. Series #10).
• Dequest 2066 also produced final bleached pulp with higher viscosity, higher yield and higher brightness (Series #11 v. Series #12).
• Kraft cooks were performed on undried softwood (pine) wood chips according to the procedure described in the Pulping Description section of the Examples using either no phosphonate (control) or using Dequest 2006 at 0.2 wt. % concentration.
• the pulp was recovered and tested and the results presented in Table 19.
• the pulp was then bleached using a DEDED sequence as described in the Bleaching Description section of the Examples using the conditions set forth in Table 19. The bleached pulp was tested during and at the end of the bleaching sequence and the results presented in Table 19.
• Handsheets were prepared from the bleached pulps of Examples 12, 13, 15 and 16 and strength properties were determined. The results are presented in Table 20. In addition to the improvements in brightness and viscosity obtained from the bleached pulp of the invention, the overall strength of the handsheets produced from bleached pulp of the invention are improved compared to the control bleached pulp.
• Viscosity cP 25.8 26.4 25.8 26.9 25.8 26.9 Basic weight, g/m ⁇ 2 62.72 61.12 60.33 60.44 61.98 61.61 Bulk, cm ⁇ 3/g 2 2 2.11 1.98 2.18 2.01 Tensile Index, N*m/g 18.6 21 18.7 21.63 17 19.27 Burst Index, kPa*m ⁇ 2/g 0.66 0.73 0.67 0.7 ⁇ 0.56 0.663 Tear Index, mN*m ⁇ 2/g 4.13 4.37 4.07 4.41 3.59 4.23 Brightness, % 91.2 91.5 81.8 83.5 92.2 92.77 Final Viscosity, cP 20.3 21.1 13.6 14.3 13.4 14 Hardwood Hardwood Softwood Sequences DED DEDED DEDED Series no.
• HW-DEDED (1%-1%-0.5%): Control 0.57 0.78 0.92 0.114 #1 2066(0.2%) 0.63 0.81 0.94 0.114 #2 HW-DE op (1%-P1%): Control 0.54 0.74 0.88 0.113 #3 2066(0.2%) 0.55 0.76 0.92 0.114 #6 HW-DE op D(1%-P1%-0.6%): Control 0.54 0.74 0.88 0.115 #4 2066(0.2%) 0.54 0.75 0.89 0.117 #7 HW-DE op P(1%-P1%-P1%): Control 0.54 0.74 0.88 0.122 #5 2066(0.2%) 0.54 0.74 0.87 0.117 #8 HW-DED (1%-1%) Control 0.59 0.79 0.92 0.108 #9 2066(0.2%) 0.59 0.79 0.93 0.108 #10 HW-DEDED (1%-1%-0.25%): Control 0.58 0.77 0.9 0.109 #11 2066(0.2%) 0.58 0.77 0.91 0.109 #12 SW-DEDED (1%-1%-0.5%) Control 1.42
• Kraft cooks were performed on undried softwood (pine) wood chips according to the procedure described in the Pulping Description section of the Examples using either no phosphonate (control) or using Dequest 2006 or Blend 78 at 0.2 wt. % concentration. The pulp was recovered and tested and the results presented in Table 22. The pulp was then bleached using a DEDED sequence as described in the Bleaching Description section of the Examples using the conditions set forth in Table 22. The bleached pulp was tested during and at the end of the bleaching sequence and the results presented in Table 22.
• Dequest 2006 and Blend 78 produced pulps with higher initial brightness, and Blend 78 produced pulp with higher initial viscosity and lower kappa number.
• Dequest 2006 and Blend 78 produced bleached pulp after the DED and DEDE stages that exhibited higher brightness.
• Dequest 2006 and Blend 78 also produced final bleached pulp with higher viscosity and final brightness.
• Kraft cooks were performed on undried softwood (aspen) wood chips according to the procedure described in the Pulping Description section of the Examples using either no phosphonate (control) or using Dequest 2006 or Blend 78 at 0.2 wt. % concentration.
• the pulp was recovered and tested and the results presented in Table 23.
• the pulp was then bleached using a DEopD and DEopP sequences as described in the Bleaching Description section of the Examples using the conditions set forth in Table 22.
• the bleached pulp was tested after the DEop stage and at the end of the DEopD and DEopP bleaching sequences and the results presented in Table 23.
• Dequest 2006 and Blend 78 produced pulps with higher initial brightness, and Blend 78 produced pulp with lower kappa number.
• Dequest 2006 and Blend 78 produced bleached pulp with higher brightness after the DEop stage.
• Dequest 2006 and Blend 78 produced final bleached pulp with higher yield and higher brightness after both the DEopD and DEopP bleaching sequences.
• Example 19 The bleached pulps of Example 19 were tested for Kajaani fiber length and physical properties and the results are presented in Table 24.
• Kraft cooks were performed on undried hardwood (aspen) wood chips according to the procedure described in the Pulping Description section of the Examples using either no phosphonate (control) or using Dequest 2016 at 0.2 wt. % concentration.
• the pulp was recovered and tested and the results presented in Table 25.
• the pulp was then bleached using a DEDED sequence (pH not adjusted) as described in the Bleaching Description section of the Examples using the conditions set forth in Table 25.
• the Dequest 2016 pulp was bleached with less ClO 2 during both the D1 and D2 stages. The bleached pulp was tested during and at the end of the bleaching sequence and the results presented in Table 25.
• Dequest 2016 produced pulps with higher initial brightness and lower kappa number.
• Dequest 2016 also produced bleached pulp with higher brightness after the D1, E1, D2 and E2 stages and comparable final brightness. It is significant that the final brightness of the Dequest 2016 bleached pulp is slightly better than the control while less ClO 2 was used because use of less bleaching chemicals has commercial advantages, including lower AOX, biological oxygen demand (BOD), and chemical oxygen demand (COD) in the discharge from the bleach unit of the pulp mill.
• BOD biological oxygen demand
• COD chemical oxygen demand
• Kraft cooks were performed on undried hardwood (aspen) wood chips according to the procedure described in the Pulping Description section of the Examples using either no phosphonate (control) or using Dequest 2016 at 0.2 wt. % concentration.
• the pulp was recovered and tested and the results presented in Table 26.
• the pulp was then bleached using a DEDED sequence (pH adjusted) as described in the Bleaching Description section of the Examples using the conditions set forth in Table 26.
• the Dequest 2016 pulp was bleached with less ClO 2 during both the D1 and D2 stages. The bleached pulp was tested during and at the end of the bleaching sequence and the results presented in Table 26.
• Dequest 2016 produced pulps with higher initial brightness and lower kappa number.
• Dequest 2016 also produced bleached pulp with higher brightness after the D1, E1, D2 and E2 stages and comparable final brightness. It is significant that the final brightness of the Dequest 2016 bleached pulp is slightly better than the control while less ClO 2 was used because use of less bleaching chemicals has commercial advantages, including lower AOX, BOD, and COD in the discharge from the bleach unit of the pulp mill.
• TABLE 26 Hardwood-DEDED Bleaching (pH adjusted) I.
• Kraft cooks were performed on undried hardwood (aspen) wood chips according to the procedure described in the Pulping Description section of the Examples using either no phosphonate (control) or using Dequest 2016 at 0.2 wt. % concentration.
• the pulp was recovered and tested and the results presented in Table 27.
• the pulp was then bleached using a OPD sequence as described in the Bleaching Description section of the Examples using the conditions set forth in Table 27. The bleached pulp was tested during and at the end of the bleaching sequence and the results presented in Table 27.
• Dequest 2016 produced pulps with higher initial brightness and lower kappa number.
• Dequest 2016 also produced bleached pulp with higher brightness after the O, P and D stages.
• Kraft cooks were performed on undried hardwood (aspen) wood chips according to the procedure described in the Pulping Description section of the Examples using either no phosphonate (control) or using Dequest 2016 at 0.2 wt. % concentration. The pulp was recovered and tested and the results presented in Table 28. The pulp was then bleached using a DEopD sequence as described in the Bleaching Description section of the Examples using the conditions set forth in Table 28. The bleached pulp was tested during and at the end of the bleaching sequence and the results presented in Table 28.
• Dequest 2016 produced pulps with higher initial brightness and lower kappa number.
• Dequest 2016 also produced bleached pulp with significantly higher brightness after the D1, Eop, and D2 stages. It is particularly significant that the final brightness of the invention is 4.1 % higher than the control as a brightness of 88.7 may enable elimination of additional bleaching steps to achieve an acceptable final brightness.
• Kraft cooks were performed on undried hardwood (aspen) wood chips according to the procedure described in the Pulping Description section of the Examples using either no phosphonate (control) or using Dequest 2016 at 0.2 wt. % concentration.
• the pulp was recovered and tested and the results presented in Table 29.
• the pulp was then bleached using a DEopP sequence as described in the Bleaching Description section of the Examples using the conditions set forth in Table 29. The bleached pulp was tested during and at the end of the bleaching sequence and the results presented in Table 29.
• Dequest 2016 produced pulps with higher initial brightness and lower kappa number.
• Dequest 2016 also produced bleached pulp with significantly higher brightness after the D1, Eop, and P stages.
• Kraft cooks were performed on undried hardwood (aspen) wood chips according to the procedure described in the Pulping Description section of the Examples using either no phosphonate (control) or using Dequest 2016 at 0.2 wt. % concentration at H-factors of 1000, 846, 693 and 539. The pulp was recovered and tested and the results presented in Table 30. Pulp from the H-factor 846 and 693 runs were then bleached using various bleaching sequences as described in the Bleaching Description section of the Examples using the conditions set forth in Tables 25-29. The viscosity of the bleached pulp was determined at the end of the bleaching sequence and the results presented in Table 30.
• Dequest 2016 produced pulps with higher initial brightness, lower kappa number, lower reject, higher yield, and higher viscosity.
• Dequest 2016 also produced bleached pulp with higher viscosity after the bleach stages of DEDED, DEDED (pH adjusted), DEop, DEopD, DEopP, O, OP, and OPD for the H-factors tested.
• the use of Dequest 2016 improved the pulps' response to bleaching sequences with respect to viscosity.
• TABLE 29 Hardwood (Aspen)-DEopP Bleaching I.
• Kraft cooks were performed on undried hardwood (aspen) wood chips according to the procedure described in the Pulping Description section of the Examples using either Dequest 2016 at 0.1 wt. % concentration or using Dequest 2066 at 0.2 wt. % concentration.
• the pulp was recovered and tested and the results presented in Table 31.
• the pulp was then bleached using a DEDED sequence (pH adjusted) as described in the Bleaching Description section of the Examples using the conditions set forth in Table 31.
• the bleached pulps were tested during and at the end of the bleaching sequence and the results presented in Table 31.
• Dequest 2016 and 2066 produced pulps with higher initial brightness and lower Kappa number.
• Dequest 2016 and 2066 also produced bleached pulp with higher brightness after the D1, E1, D2 and E2 stages and comparable final brightness. It is significant that the final brightness is comparable while less ClO 2 was used because use of less bleaching chemical has the aforementioned commercial advantages. Comparing Table 31 with Table 26, it is also shown that 0.2% Dequest 2016 produces brighter pulp than 0.1% Dequest 2016.
• Kraft cooks were performed on undried hardwood (aspen) wood chips according to the procedure described in the Pulping Description section of the Examples using either Dequest 2016 at 0.1 wt. % concentration or using Dequest 2066 at 0.2 wt. % concentration.
• the pulp was recovered and tested and the results presented in Table 32.
• the pulp was then bleached using a DEopD sequence as described in the Bleaching Description section of the Examples using the conditions set forth in Table 32. The bleached pulps were tested during and at the end of the bleaching sequence and the results presented in Table 32.
• the data in Table 32 demonstrates that Dequest 2016 and 2066 produced pulps with higher initial brightness and lower Kappa number. Dequest 2016 and 2066 also produced bleached pulp with significantly higher brightness after each stage. It is significant that the final brightness of the invention is 3.9-4.1% higher than the control as a brightness of 88.5-88.7 may enable elimination of additional bleaching steps to achieve an acceptable final brightness. Comparing Table 32 with Table 28, it is also shown that 0.1% and 0.2% Dequest 2016 produce equivalent brightness. TABLE 31: Hardwood (Aspen)-DEDED Bleaching (pH adjusted) I.
• Kraft cooks were performed on undried hardwood (aspen) wood chips according to the procedure described in the Pulping Description section of the Examples using either Dequest 2016 at 0.1 wt. % concentration or using Dequest 2066 at 0.2 wt. % concentration.
• the pulp was recovered and tested and the results presented in Table 33.
• the pulp was then bleached using a DEopP sequence (pH adjusted) as described in the Bleaching Description section of the Examples using the conditions set forth in Table 33.
• the bleached pulps were tested during and at the end of the bleaching sequence and the results presented in Table 33.
• Kraft cooks were performed on undried hardwood (aspen) wood chips according to the procedure described in the Pulping Description section of the Examples using either no added compound of the invention (control) or compound 4NHMP, DTPA, Blend 83A, and Blend 84 at 0.2 wt. % concentration or Blend 86 at 0.1 wt. % concentration.
• the pulp was recovered and tested and the results presented in Table 34.
• the pulp was then bleached using a DEDED sequence (pH adjusted) as described in the Bleaching Description section of the Examples using the conditions set forth in Table 34. The bleached pulps were tested during and at the end of the bleaching sequence and the results presented in Table 34.
• the data in Table 34 demonstrates that compounds of the invention tested produced pulps with higher initial brightness and lower kappa number.
• the compounds of the invention tested also produced bleached pulp with higher brightness after the D1, E1, D2, E2 and D3 stages.
• the improvement in final brightness is significant.
• the data in Table 34 further demonstrates that the most significant improvement in final brightness is achieved with compound 44NHMP or the blend of compound 44NHMP and Dequest 2016 (Blend 83A).
• TABLE 33 Hardwood (Aspen)-DEopP Bleaching I.
• the digester equipment consisted of seven Parr bomb reactors (approx. 1 L) in a carousel that were rotated through a temperature-controlled oil bath. Aspen wood chips and white liquor used in the Kraft cooks were obtained from a commercial pulp mill located in the Upper Midwestern United States. The wood chips used were hand picked to reduce variability. Pulping conditions were: liquor:wood weight ratio of 4:1, 16% active alkali and 26.7% sulfidity. The digester temperature was ramped from ambient temperature to 170°C in approximately 72 minutes. The H-factor was varied in the cooks conducted.
• Total Yield (total solid weight of air-dried pulp recovered*100)/(weight of OD wood chip used).

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